To discuss the macromolecular structure and properties of lignin, the complementary use of solid- and liquid-state nuclear magnetic resonance (NMR) combined with a specific C-13-enrichment technique may provide useful information. The C-13-enriched lignin was prepared by administering [guaiacyl ring-5(G5)-C-13]-coniferin to a growing Ginkgo biloba L shoot. The C-13-enriched cellulolytic enzyme lignin (EL) and its acetate prepared from the ginkgo shoot were examined by solid- and liquid-state C-13 NMR spectroscopy. The C-13 NMR spectrum derived only from the G5 carbon was obtained as a difference spectrum based on the spectra of the G53-C-13 enriched and un-enriched (UE) samples. The condensed structures, including the enriched G5-carbon, were evaluated using difference spectra. The chemical shifts of the enriched G5 carbon in both the solid- and liquid-state C-13 NMR spectra agreed with each other in principle. The quantitative ratio of the condensed and uncondensed structures at G5 was found to be larger by solid-state cross polarization/magic angle spinning (CP/MAS) NMR than by liquid-state NMR.